Insight into the π‐hole···π‐electrons tetrel bonds between F₂ZO (Z = C, Si, Ge) and unsaturated hydrocarbons

Abstract

The intermolecular π‐hole···π‐electrons interactions between F2ZO (Z = C, Si, Ge) molecules and unsaturated hydrocarbons including acetylene, ethylene, 1,3‐butadiene and benzene were constructed to reveal the differences of tetrel bonds forming by carbon and heavier tetrel atoms. The ab initio computation in association with topological analysis of electron density, natural bond orbital, and energy decomposition analysis demonstrate that the strength of Si···π and Ge···π tetrel bonds is much stronger than that of C···π tetrel bonds. The Si···π and Ge···π tetrel bonds exhibit covalent or partially covalent interaction nature, while the weak C···π tetrel bonds display the hallmarks of noncovalent interaction, the electrostatic interaction is the primary influencing factor. The Si···π and Ge···π interactions are determined by both the σ‐ and π‐electron densities, while the C···π interactions are dominated mainly by the π‐electron densities. The π‐hole···π‐electrons tetrel bonds are dominated by electrostatic interaction, and polarization has a comparable contribution in the Si···π and Ge···π tetrel bonds.

Dual Geometry Schemes in Tetrel Bonds: Complexes between TF4 (T = Si, Ge, Sn) and Pyridine Derivatives

“…However, this bond did not substantially alter the geometry of the tetrel-containing molecule. Another bonding scenario where this out-of-plane situation can occur is the planar F 2 T=O molecule [26,65,66,67] or R 2 T=CH 2 [25]. These sorts of geometries typically result in weaker binding, as for example, the replacement of TF 4 by TF 2 =CF 2 (T = Si, Ge, Sn) [25].…”

Crystallographic and Computational Characterization of Methyl Tetrel Bonding in S-Adenosylmethionine-Dependent Methyltransferases

“…As in the case of halogen, chalcogen, and pnictogen bonds, tetrel bonds are much stronger for elements in lower rows of the periodic table, e.g., Si and Ge. For this reason, the majority of computational work [ 67 , 68 , 69 , 70 , 71 , 72 , 73 , 74 , 75 , 76 , 77 ] has been dedicated to these stronger interactions. However, it is to the nominally weaker carbon tetrel bonds that this work is devoted, due in part to their prevalence in biological systems.…”

Versatility of the Cyano Group in Intermolecular Interactions

“…The same sort of tetrel bonding through a C π-hole occurs in other systems as well [ 32 , 33 ]. This idea is not restricted to C but occurs on other sorts of atoms—for example, the S atom of SO 2 [ 31 ] or SO 3 [ 34 ] or the central O of ozone [ 35 ] or for tetrel T atoms larger than C, as in F 2 TO [ 36 , 37 , 38 ], or the N atom of the -NO 2 group [ 39 ]. Other planar examples involve triel (Tr) atoms in TrR 3 , where R indicates some substituent [ 40 , 41 ].…”